Reactive fine particles

ABSTRACT

A reactive fine particle includes one or more functional compounds A or its precursors having a maximal size of less than 2 microns, adapted for synthesis, modification, curing, cross-linking, secession and/or initiating of polymerization of polymers; and one or more inert particles B having at least the maximal size of 2 microns and carrying said functional compounds A at its outer surface and/or in its inner portion. The compounds A to inert particles B weight ratio is ranging from 0.01A:100B to 50A:100B.

FIELD OF THE INVENTION

The present invention generally relates to reactive fine particles andespecially to fine latent curing agents; to a method for theirproduction and to any use or end product comprising said novel particlesor said method.

BACKGROUND OF THE INVENTION

Latent curing agents are solid low molecular weight chemicals that aredispersed in monomers, oligomers and polymers or mixtures thereof. Thosechemicals are practically inactive at ambient temperature and becomeactive at elevated temperatures. When activated, the dispersed solidparticles of latent curing agent melt and react or initiatepolymerization with polymers to form a cross-linked polymeric network.

A thermoset polymer is a polymer that doesn't melt when heated. Thetypical latent curing agents in thermosets, especially in epoxy systems,are solid fine powders that are dissolved in the epoxy matrix only abovecritical temperatures.

Epoxy based thermosets are cost effective matrices known for their lowviscosity, excellent chemical and thermal properties, costeffectiveness, excellent adhesion to metals, ceramics and plastics, easeof application, low toxicity, wide spectrum of resins, diluents,modifiers and curing agents. The most popular epoxy resins for highperformance applications are Diglycidyl ethers of bisphenol A(hereinafter ‘DGEBA’), epoxy phenol Novolacs (hereinafter ‘EPN’), epoxycresol Novolacs (hereinafter ‘ECN’), Diglycidyl ethers of bisphenol F(hereinafter ‘DGEBF’), and bisphenol A based Novolacs.

Epoxy is the major building block of most high-end adhesives, legendmarking inks, solder masks and hole plugging pastes. The most commonlatent curing agent for epoxy resins are urea derivatives, imidazoles,modified amines, and dicyandiamide (hereinafter ‘DICY’), which is acommercially available ingredient in high-end electronic applications,such as adhesives, PCBs manufacturing, solder masks and hole plugginginks. DICY is characterized by a significant latency (pot life) andoutstanding final properties of the cured matrix. It is activated attemperatures in the range of 160-170° C. without a catalyst and in therange of 120 to 150° C. with catalyst. The catalyst usually has negativeimpact on a pot life of the mixed formula.

Ink jet technology enables a very precise digital printing and providesfor relatively small dots of liquid or molten material. Digital printingof high performance polymers adapted for marking, protection, coating,encapsulation and definition in electronic manufacturing has become areality in recent years. The aforementioned ink is characterized by alow viscosity, less than 15 Cp at jetting temperature. When solidparticles are used, their maximal size must be sub-micron, preferablyless than 700 nm. These particles are usually selected from fillers,pigments, curing agents, rheology modifiers and matting agents.Thermoset inkjet inks, and particularly epoxy-containing ink-jet ink arelatent high performance latent resins and particularly epoxy-containingparticles of latent curing agent such DICY. Nevertheless, the finestcommercially available DICY powders are characterized by an averageparticle size of 4 to 6 micron, thus their use in ink-jet application isavoided. A sub-micron latent curing agent is hence a critical componentfor high performance digital printing inks and its commercialavailability ass a long felt need.

BRIEF DESCRIPTION OF THE INVENTION

In order to understand the invention and to see how it may beimplemented in practice, a plurality of embodiments shall now bedescribed, in a non-limiting manner only, with reference to theaccompanying drawings, in which

FIG. 1 schematically illustrates a top view of a portion of the reactivefine particle according to one embodiment of the present invention;

FIG. 2 schematically illustrates a lateral cross section of a portion ofthe reactive fine particle according to said embodiment of the presentinvention;

FIG. 3 schematically illustrates a lateral cross section of a portion ofthe reactive fine particle according to yet another embodiment of thepresent invention, wherein a multi-laminar heterogamous coating isprovided;

FIG. 4 schematically illustrates a lateral cross section of a portion ofthe reactive fine particle according to another embodiment of thepresent invention wherein the reactive particles are located in theinner and the outer portion of the inert particle; and

FIG. 5 schematically illustrates a lateral cross section of a reactivefine particle according to another embodiment of the present invention,wherein at step A is comprises a physical support of the inert particle,and at the subsequent step B is comprises only the reactive particles.

SUMMARY OF THE INVENTION

It is hence the object of the present invention to provide a costeffective and novel reactive fine particle; comprising one or morefunctional compounds A or its precursors having a maximal size lower 2microns; adapted for synthesis, modification, curing, cross-linking,secession and/or initiating of polymerizations of polymers, and one ormore inert particles B having a maximal size lower 2 microns carryingsaid functional compounds A at the outer surface and/or in its innerportion; wherein said compounds A to inert particles B weight ratio isranging from 0.01A:100B to 50A:100B.

According to one embodiment of the present invention, the aforementionedreactive fine particle defined above are adapted for curing thermoseticpolymers; wherein at least a portion of the functional compounds arecuring agents or latent curing agents adapted to initiate cross linkingand/or polymerization said thermoset polymers.

According to yet another embodiment of the present invention, a liquidthermosetting compound is hereto provided, and is adapted to be cured bythe curing agents as defined above. This liquid thermosetting compoundis comprised of the reactive fine particles A, inert particles B andvarious compounds selected in a non-limiting manner from thermosettingresins, thermoplastic resins, nano-particles, wetting agents, reactivediluents, impact modifiers, flexibilizers, heat stabilizers, surfacetension modifiers, adhesion promoter, flame retardants, matting agents,rheology modifiers, dispersants or any combination thereof.

It is in the scope of the present invention wherein the aforementionedliquid thermosetting compound is further adapted for applications inmicroelectronic devices manufacturing selected from dielectrics,resistors, optical waveguides, conductive modules, capacitance layers,adhesives, protective coatings, encapsulants or any combination thereof.It is also in the scope of the present invention wherein theaforementioned liquid thermosetting compound is adapted for ink jet inksand/or ink jet printers; characterized by a viscosity lower 50 Cp atapplication temperature, surface tension lower 80 dyn/cm at applicationtemperature, and glass transition temperature of cured ink of greaterthan 120° C. The liquid thermosetting is preferably adapted to protect,mark, seal, encapsulate, define, and/or insulate electronic circuitsfrom their environment and/or form aggressive media. More specifically,this liquid thermosetting compound according to yet another embodimentof the present invention is adapted to bond electronic, electric, opticand/or electro optic devices; to mark and notate features on the outerlayers of PCB and/or the surface of discrete compounds; to define thefeature of capacitors, resistors and/or conductors on a PCB layer.

It is a second object of the present invention to provide a costeffective and novel method for producing reactive fine particles asdefined in any of the above. This method comprising inter alia the stepsof (a) dissolving one or more functional compounds A or its precursorshaving a maximal size lower 2 microns in a solvent to form a clearsolution; (b) admixing one or more inert particles B having a maximalsize lower 2 microns with the solution obtained above to form ahomogenized dispersion; (c) precipitating said functional compounds as alayer or in the form of small crystals onto and/or into the surface ofsaid inert particles; (d) evaporating said solvent; (e) drying orconcentrating the same; in the manner that reactive fine particlescomprising said compounds A and inert particles B in a weight ratiowhich is ranging from 0.01A:100B to 50A:100B is obtained.

According to one embodiment of the present invention, the aforementionedmethod is provided wherein the deposition of the functional compounds Aonto the inert particles B is provided by means selected fromintroducing of at least one another solvent to the said admixture;changing the temperature; pH shifting; altering electrolytesconcentration, spraying agent solution on filler particles, or anycombination thereof.

Additionally or alternatively, this method is additionally comprised ofthe step of stabilizing the obtained slurry by means of admixing asufficient measure of dispersing agents and/or rheology modifiers.Moreover, this method is also provided useful wherein at least a portionof the precursors of the functional compounds A are admixed with theinert particles B at the reaction medium.

According to another embodiment of the present invention, theaforementioned method is provided for producing reactive fine particles,wherein the inert particles B are coated in at least a significantportion of their surface with functional compounds A. This methodcomprising inter alia the steps of (a) admixing at least one functionalcompound or its precursors in a solvent to form a clear solution; (b)spraying the same towards particles of the inert filler, having maximalparticle size of 2 microns; and then, (c) removing said solvent, in themanner that reactive fine particles comprising dried inert particlescoated by functional compounds is obtained. The method is alsoapplicable wherein the reactive fine particles obtained comprisinghomogeneous or heterogeneous functional compounds compositions; and/orwherein monolayers or multilayers of functional compounds characterizethe reactive fine particles obtained.

DETAILED DESCRIPTION OF THE INVENTION

The following description is provided, alongside all chapters of thepresent invention, so as to enable any person skilled in the art to makeuse of said invention and sets forth the best modes contemplated by theinventor of carrying out this invention. Various modifications, however,will remain apparent to those skilled in the art, since the genericprinciples of the present invention have been defined specifically toprovide sub micron reactive particles, a method for their production andany use or end product comprising said novel particles or said method.

The term ‘fine particle’ is referring according to the preset inventionto any small particle; compound, matrix or a composition encapsulated,barriered, crystallized or packed in a predetermined 3D environmentcharacterized by an Maximal external diameter lower 2 micrometer. Morepractically the powder should have maximal aggregate (conglomerate) sizeof 700 nm.

The term ‘reactive fine particle’ is referring according to the presetinvention to fine particle, either prime particle or aggregate oragglomerate as defined above, comprising at least one type of inertparticle (hereinafter ‘B’) and at least type of functional component(hereinafter ‘A’), wherein the maximal size of said particle is lessthan 2 micrometer (e.g., between 200 to 2000 nm). Component A is inphysical communication with said inert particle B. It is further in thescope of the present invention wherein said reactive fine particle iscomprised of various types of functional components (As) and inertparticles (Bs), differ by their size, 3D structure, surface activity,reactivity, latency property, chemical composition, specific area or anyother physical, chemical or biological properties. It is further in thescope of the present invention wherein said functional components (As)are only temporary comprised of at least a portion of the inertparticles (Bs), in the manner the content of the said inert particles inthe end product is significantly lower than its content at the beginningof the production process. It is still in the scope of the presentinvention wherein the nature of the said portion of inert particles isdiffering, altering or changing along the said production process.

According to the present invention, the term ‘polymer’ is refereeinghereinafter to any monomer, oligomer or polymer, their mixture, or toany combination thereof. Moreover, this term is also referring to blockpolymers, co-polymers and to all product and by-products ofpolymerization reactions.

According to one embodiment of the present invention, the aforementionedfine particles are comprised of at least one inert particle B that iseither inorganic material, e.g., comprising mineral metal oxides,mineral natural fillers, synthetic metal oxides, ceramics, metalliccompositions, glass or sol-gel matrices, chemical element or any mixturethereof, or organic material, such as cellulose, natural polymer,synthetic polymer or any mixture thereof. The said fine powder B ischaracterized by a specific surface area ranges from about 1 to 300m²/g. According to yet another embodiment of the present invention, saidpowder is characterized by a specific surface area ranges from about 10to about 50 m²/g.

The said fine particles may further comprised of at least one latentreactive composition A (e.g., a solid latent curing agent) which isdissolved in the solution in a weight ratio ranging from 0.01 A to 100B; to 50 A to 100 B. According to yet another embodiment of the presentinvention, the said ratio is ranging form 5 A to 100 B; to 40A to 100 B.It is acknowledged in this respect that additives of any type arepotentially comprised in the said particle. Hence, presence ofcommercially available dispersing agents and rheology controlling agentsis recommended to avoid agglomeration during concentration and storage.

The carrier inert particle B may be selected in a non-limiting mannerform one or more of the following criteria: having a specific surfacearea between 1 to 300 m²/g., wherein the most favorable powder is theone characterized by a specific surface area ranging between 10 and 50m²/g; since it is non-abrasive, and hence avoid damage to applicationtooling, especially to an ink-jet print head. Moreover, the carrier ispreferably non-corrosive; it has a good thermal stability and chemicalresistance; it is not reacting with the reactive particle and with themonomers, oligomers, polymers, solvents and/or additives in the ink. Theinert particle B is further of sub-micron prime particle size, mostfavorably between 0.03 to 0.5 micron mean diameter; the maximalagglomerate size is 2 micron. It does not tend to deagglomerate or todisintegrate under milling; and/or it has a good compatibility with themonomers, oligomers, polymers, solvents and additives in the ink.Typical powders that meet these criteria are sulfates, e.g., BaSO₄ orCaSO₄, carbonates such as CaCO₃, talc, kaolin, mica, silicates, andcarbon black and synthetic silica.

The carrier medium is optimized for effectively dissolving thefunctional component A and is selected in a non-limiting manner form oneor more of the following criteria: it is not toxic or is characterizedby a very low toxicity; it is cost effective since it is at leastpartially re-usable and/or recycledable; it is a good solvent for thereactive latent curing agent id present; it has a low boiling point anda low specific heat of evaporation; and further, it is practically nonreactive with either the inert or the reactive particles.

Reference is made now to FIG. 1, presenting a simplified top viewreactive fine particles according to the present invention, wherein anrelatively large inert particle B (1) is coated by a plurality offunctional component A (see 2 for example). Said functional component(2) was crystallized on top the inert particle (1) and is characterizedby a specific, defined and relative crystal 3D structure.

Reference is made now to FIG. 2, presenting a lateral cross-section ofone portion of homogeneously coated reactive fine particle (20). Saidportion comprising a central inert particle (1) and a plurality offunctional components (see 2 for example). Said functional componentsmay by either homogenous or heterogeneous nature, morphology or size,and may be set as an individual crystalline (portion a) or may beattached physically or chemically one to the others so a thin coating isprovided (portion b).

Reference is made now to FIG. 3, presenting a lateral cross-section ofone portion of heterogeneously coated reactive fine particle (30). Saidportion comprising a central inert particle (1) and a plurality offunctional components of type 2A (first and internal coating layer),type 2B (second coating layer) and type 2C (third and external coatinglayer). It is in the scope of the present invention wherein such aheterogeneous system is arranged as a plurality of layers in the mannerat least one layer is homogeneous; a conglomerate comprising two or moretypes of reactive particles or any combination or mixture thereof.

Here, the three coating layer perform a contentious multi-componentlayer. Nevertheless, a porosive or other discontinuous layered orembedded structures are easily to be tailor made according to thedescription of the present invention.

Reference is made now to FIG. 4, presenting a lateral cross-section ofone portion of homogeneously embedded reactive fine particle (40). Saidportion comprising a central inert particle (1) and a plurality offunctional components, some are entrapped, immobilized, encapsulated,soaked, doped or bonded into the inner portion of the inert particle(2D); and some are coated on the outer rim of the inert particle (2E). Areactive fine particle incorporating either homogenous or heterogeneoussystems located in the inner portion, outer portion or a combinationthereof is also possible according to the description of the presentinvention

Reference is made now to FIG. 5, presenting a lateral cross-section ofone portion of homogeneously coated reactive fine particle (50).Illustration 5A presents the said portion, wherein it is initiallycomprised of a central inert particle (1) and a plurality of functionalcomponents (see 2 for example). Illustration 5B however presents thesaid portion, whereat the inert particle is removed (51) in he manner itis currently comprised of the thin layer of the functional components.The removal of the said inert particle (1) in step (51) is provided bymany known techniques of the art, such as physical treatments(temperature change, UV emission, sonication etc.), chemical reactions(pH shifting in the manner solubility is altered, oxidation,liquid-liquid extraction, etc), controlled biological response etc. Sucha vehicle-like vesicle may be further processed in any manner.

It is well acknowledged in this respect that the precursors of thereactive fine particles are being admixed with the filler at thereaction medium and not the reactive fine particles themselves.Reference for that is made by U.S. Pat. No. 6,235,865 to Shimizu et al.,which discloses phosphonium borate compounds useful as a curing catalystin epoxy and other resin compositions, and U.S. Pat. No. 6,492,437 toMusa et al., which teaches for solvent-based processes for producinglatent curing catalysts without causing an extreme exotherm.

It is in the scope of the present invention to provide a useful methodfor the production of the reactive fine particles A as defined in any ofthe above. Hence, the general approach for the production of thereactive fine particles according to the present invention is a simpleprocess comprised inter alia of the following five steps: (a) dissolvingat least one reactive fine particles or its precursors, characterized byfine particles, in a solvent to form a clear solution; (b) admixing aninert filler B having maximal particle size of 2 microns with thesolution obtained above to form a homogenized dispersion; (c)precipitating said reactive fine particles as a layer or in the form ofsmall crystals onto said filler surface and/or inside the internalporosity of said filler; (d) evaporating said solvent; and lastly, (e)drying or concentrating the same.

Additionally, a method for producing coated filler particles is heretoprovided. Those filler particles B are coated the reactive fineparticles A in at least a significant portion of their surface. Saidmethod comprising inter alia the steps of admixing at least one reactivefine particle or its precursors in a solvent to form a clear solution,and then spraying the same towards particles of the inert filler, havingmaximal particle size of 2 microns. After removing said solvent, driedcoated filler is obtained. The spraying is referring for any applicablemeans for jetting components A over components B, such as using anatomizer and a stream of hot carrier of air or gas.

It is in the scope of the present invention wherein sprayed suspensionor solution comprising the reactive fine particle A or its precursors issprayed onto a stream of B powder so a 0.01A:100B to 50A:100B coateddispersion is provided.

It is further acknowledged in this respect that since the surface areathe inert particle B is high and the amount of the functional componentA is limited, crystals or films of functional component A are small orthin so crystallization of particles to a non-desired big size iseffectively limited.

The presence of organic dispersant (e.g., dispersing agent), assuresthat the particles are covered by a layer that minimize the tendency tore-agglomerate. The powder or slurry is then milled in pearl mill, sandmill or attritor in the presence of additional amount of dispersingagent to a smooth paste, so a fine particles are obtained, such as fineparticles carrying a latent curing agents. Polymer resin (epoxy forexample), and rheology modifier (e.g., fumed silica) can be incorporatedin order to control rheology and prevent re-agglomeration.

It is in the scope of the present invention wherein the reactive fineparticles as defined in any of the above are applicable in the variouselectronic technologies, especially for electronic and/ormicroelectronic and/or optical components or devices manufacturingprocesses suitable to be applied by ink jet technology. Morespecifically, the electronic technologies defined above may be selectedfrom solder masks, dielectrics, resistors, optical waveguides,conductive modules, capacitance layers, adhesives, protective coatings,encapsulants or any combination thereof.

EXAMPLE 1

To prepare reactive fine particles useful as latent curing agents, thefollowing formulation was prepared. The following ingredient whereeffectively admixed: 6 parts EPN (EEW=174); 24 parts DGEBF (EEW=170); 5parts acrylated oligomers having functionality of 1 and viscosity of 5Cp; 3 parts acrylated oligomer having functionality of 2; 3 parts ofacrylated oligomer with functionality of 3; one part acrylated epoxy; 4parts free radical photinitiator; 9 parts BaSO₄ inert filler havingparticle size of 40 nm and surface area of 30 m²/g; 5 parts ofdispersant; 0.2 parts organic peroxide; 25 parts glycol ether solventsmixture; 2.5 parts micronized DICY having average article size of 6microns; 8 parts of melamine formaldehyde (MF) resin; 0.5 parts ofwetting agents. The formulation was milled in pearl mill to disperse thesolids. Ink jet ink was prepared from the same.

EXAMPLE 2

To enable continuous filtration of the ink obtained above, as requiredin industrial ink jet machines and enable introducing into the printhead, a process of deposition of DICY on particles smaller than 2 μm wasdeveloped. DICY was slowly precipitated onto BaSO₄ fine particles fromsaturated organic or aqueous solution, and stabilized by reologyadditives and dispersant. The obtained slurry was milled with epoxyresins, dispersants and solvents to form an ink precursor. The resinsand dispersant keep the rheology in a state that blocks re-agglomerationand DICY crystals growth. Milling was performed in a Dyno Mill,( Beadsize 0.4 mm, 2000 RPM, Retention time of about 12 minutes), until thislow viscosity concentrate could be easily filtered through 2 μm glassfiber filter.

1. A reactive fine particle; comprising a. one or more functionalcompounds A or its precursors having a maximal size of less than 2microns; adapted for synthesis, modification, curing, cross-linking,secession and/or initiating of polymerization of polymers, and b. one ormore inert particles B having a least the maximal size of 2 micronscarrying said functional compounds A at the outer surface and/or in itsinner portion; wherein said compounds A to inert particles B weightratio is ranging from 0.01 A:100B to 50A:100B.
 2. The reactive fineparticle according to claim 1 adapted for curing thermosetic polymers;wherein at least a portion of the functional compounds are curing agentsor latent curing agents adapted to initiate cross linking and/orpolymerization said thermoset polymers.
 3. A liquid thermosettingcompound adapted to be cured by the curing agents as defined in claim 2,comprising reactive fine particles A, inert particles B and compoundsselected from thermosetting resins, thermoplastic resins,nano-particles, wetting agents, reactive diluents, impact modifiers,flexibilizers, heat stabilizers, surface tension modifiers, adhesionpromoter, flame retardants, matting agents, rheology modifiers,dispersants or any combination thereof.
 4. The liquid thermosettingcompound according to claim 3, adapted for applications inmicroelectronic devices manufacturing selected from dielectrics,resistors, optical waveguides, conductive modules, capacitance layers,adhesives, protective coatings, encapsulants or any combination thereof.5. The liquid thermosetting compound according to claim 4 for ink jetinks and/or ink jet printers; characterized by a viscosity lower 50 Cpat application temperature, surface tension lower 80 dyn/cm atapplication temperature, and glass transition temperature of cured inkof greater than 120° C.
 6. The liquid thermosetting according to claim4, adapted to protect, mark, seal, encapsulate, define, and/or insulateelectronic circuits from their environment and/or form aggressive media.7. The liquid thermosetting according to claim 6, adapted to bondelectronic, electric, optic and/or electro optic devices.
 8. The liquidthermosetting according to claim 6, adapted to mark and notate featureson the outer layers of PCB and/or the surface of discrete compounds. 9.The liquid thermosetting according to claim 6, adapted to define thefeature of capacitors, resistors nd/or conductors on a PCB layer.
 10. Amethod for producing reactive fine particles as defined in claim 1,comprising inter alia the steps of: a. dissolving one or more functionalcompounds A or its precursors having a maximal size lower 2 microns in asolvent to form a clear solution; b. admixing one or more inertparticles B having a maximal size lower 2 microns with the solutionobtained above to form a homogenized dispersion; c. precipitating saidfunctional compounds as a layer or in the form of small crystals ontoand/or into the surface of said inert particles; d. evaporating saidsolvent; e. drying or concentrating the same; in the manner thatreactive fine particles comprising said compounds A and inert particlesB in a weight ratio which is ranging from 0.01A:100B to 50A:100B isobtained.
 11. The method according to claim 10, wherein deposition ofthe functional compounds A onto the inert particles B is provided bymeans selected from introducing of at least one another solvent to thesaid admixture; changing the temperature; pH shifting; alteringelectrolytes concentration, spraying agent solution on filler particles,or any combination thereof.
 12. The method according to claim 10,additionally comprising the step of stabilizing the obtained slurry bymeans of admixing a sufficient measure of dispersing agents and/orrheology modifiers.
 13. The method according to claim 10, wherein atleast a portion of the precursors of the functional compounds A areadmixed with the inert particles B at the reaction medium.
 14. A methodfor producing reactive fine particles, wherein the inert particles B arecoated in at least a significant portion of their surface withfunctional compounds A; said method comprising inter alia the steps ofa. admixing at least one functional compound or its precursors in asolvent to form a clear solution; b. spraying the same towards particlesof the inert filler, having maximal particle size of 2 microns; andthen, c. removing said solvent, in the manner that reactive fineparticles comprising dried inert particles coated by functionalcompounds is obtained.
 15. The method according to claim 14, wherein thereactive fine particles obtained comprising homogeneous or heterogeneousfunctional compounds compositions.
 16. The method according to claim 14,wherein the reactive fine particles obtained are characterized bymonolayers or multilayers of functional compounds.